Refine
Document Type
- Article (reviewed) (17) (remove)
Language
- English (17)
Has Fulltext
- no (17) (remove)
Is part of the Bibliography
- yes (17)
Keywords
- Lithiumbatterie (4)
- Brennstoffzelle (2)
- Durchfluss (2)
- Polymere (2)
- Cantera (1)
- Diffusion (1)
- Elektrode (1)
- Elektrolyt (1)
- Gas (1)
- Hochtemperaturbrennstoffzelle (1)
Institute
- Fakultät Maschinenbau und Verfahrenstechnik (M+V) (17) (remove)
Open Access
- Closed Access (6)
- Open Access (4)
- Diamond (1)
A two-dimensional single-phase model is developed for the steady-state and transient analysis of polymer electrolyte membrane fuel cells (PEMFC). Based on diluted and concentrated solution theories, viscous flow is introduced into a phenomenological multi-component modeling framework in the membrane. Characteristic variables related to the water uptake are discussed. A Butler–Volmer formulation of the current-overpotential relationship is developed based on an elementary mechanism of electrochemical oxygen reduction. Validated by using published V–I experiments, the model is then used to analyze the effects of operating conditions on current output and water management, especially net water transport coefficient along the channel. For a power PEMFC, the long-channel configuration is helpful for internal humidification and anode water removal, operating in counterflow mode with proper gas flow rate and humidity. In time domain, a typical transient process with closed anode is also investigated.
The state-of-the-art electrochemical impedance spectroscopy (EIS) calculations have not yet started from fully multi-dimensional modeling. For a polymer electrolyte membrane fuel cell (PEMFC) with long flow channel, the impedance plot shows a multi-arc characteristic and some impedance arcs could merge. By using a step excitation/Fourier transform algorithm, an EIS simulation is implemented for the first time based on the full 2D PEMFC model presented in the first part of this work. All the dominant transient behaviors are able to be captured. A novel methodology called ‘configuration of system dynamics’, which is suitable for any electrochemical system, is then developed to resolve the physical meaning of the impedance spectra. In addition to the high-frequency arc due to charge transfer, the Nyquist plots contain additional medium/low-frequency arcs due to mass transfer in the diffusion layers and along the channel, as well as a low-frequency arc resulting from water transport in the membrane. In some case, the impedance spectra appear partly inductive due to water transport, which demonstrates the complexity of the water management of PEMFCs and the necessity of physics-based calculations.
Passive hybridization refers to a parallel connection of photovoltaic and battery cells on the direct current level without any active controllers or inverters. We present the first study of a lithium-ion battery cell connected in parallel to a string of four or five serially-connected photovoltaic cells. Experimental investigations were performed using a modified commercial photovoltaic module and a lithium titanate battery pouch cell, representing an overall 41.7 W-peak (photovoltaic)/36.8 W-hour (battery) passive hybrid system. Systematic and detailed monitoring of this system over periods of several days with different load scenarios was carried out. A scaled dynamic synthetic load representing a typical profile of a single-family house was successfully supplied with 100 % self-sufficiency over a period of two days. The system shows dynamic, fully passive self-regulation without maximum power point tracking and without battery management system. The feasibility of a photovoltaic/lithium-ion battery passive hybrid system could therefore be demonstrated.
The accurate diagnosis of state of charge (SOC) and state of health (SOH) is of utmost importance for battery users and for battery manufacturers. State diagnosis is commonly based on measuring battery current and using it in Coulomb counters or as input for a current-controlled model. Here we introduce a new algorithm based on measuring battery voltage and using it as input for a voltage-controlled model. We demonstrate the algorithm using fresh and pre-aged lithium-ion battery single cells operated under well-defined laboratory conditions on full cycles, shallow cycles, and a dynamic battery electric vehicle load profile. We show that both SOC and SOH are accurately estimated using a simple equivalent circuit model. The new algorithm is self-calibrating, is robust with respect to cell aging, allows to estimate SOH from arbitrary load profiles, and is numerically simpler than state-of-the-art model-based methods.
Aqueous lithium–oxygen batteries are promising candidates for electric energy storage. In this paper we present and discuss a multiphase continuum model of an aqueous lithium–oxygen single cell including reactions and transport in a porous gas diffusion electrode (GDE). The model is parameterized using in-house half-cell experiments and available literature data on aqueous electrolytes. We validate our transport model with cyclic voltammetry and electrochemical impedance spectroscopy measurements over a wide range of temperatures (25, 40, 55 °C) and electrolyte concentrations (0.1–2 M). We observe very good agreement between simulations and measurements during oxygen reduction conditions. A sensitivity analysis of the validated model demonstrates the influence of the porous structure on GDE performance and gives directions for the future development of electrodes.
Seven cell design concepts for aqueous (alkaline) lithium–oxygen batteries are investigated using a multi-physics continuum model for predicting cell behavior and performance in terms of the specific energy and specific power. Two different silver-based cathode designs (a gas diffusion electrode and a flooded cathode) and three different separator designs (a porous separator, a stirred separator chamber, and a redox-flow separator) are compared. Cathode and separator thicknesses are varied over a wide range (50 μm–20 mm) in order to identify optimum configurations. All designs show a considerable capacity-rate effect due to spatiotemporally inhomogeneous precipitation of solid discharge product LiOH·H2O. In addition, a cell design with flooded cathode and redox-flow separator including oxygen uptake within the external tank is suggested. For this design, the model predicts specific power up to 33 W/kg and specific energy up to 570 Wh/kg (gravimetric values of discharged cell including all cell components and catholyte except housing and piping).
The DMFC is a promising option for backup power systems and for the power supply of portable devices. However, from the modeling point of view liquid-feed DMFC are challenging systems due to the complex electrochemistry, the inherent two-phase transport and the effect of methanol crossover. In this paper we present a physical 1D cell model to describe the relevant processes for DMFC performance ranging from electrochemistry on the surface of the catalyst up to transport on the cell level. A two-phase flow model is implemented describing the transport in gas diffusion layer and catalyst layer at the anode side. Electrochemistry is described by elementary steps for the reactions occurring at anode and cathode, including adsorbed intermediate species on the platinum and ruthenium surfaces. Furthermore, a detailed membrane model including methanol crossover is employed. The model is validated using polarization curves, methanol crossover measurements and impedance spectra. It permits to analyze both steady-state and transient behavior with a high level of predictive capabilities. Steady-state simulations are used to investigate the open circuit voltage as well as the overpotentials of anode, cathode and electrolyte. Finally, the transient behavior after current interruption is studied in detail.
Modeling and simulation play a key role in analyzing the complex electrochemical behavior of lithium-ion batteries. We present the development of a thermodynamic and kinetic modeling framework for intercalation electrochemistry within the open-source software Cantera. Instead of using equilibrium potentials and single-step Butler-Volmer kinetics, Cantera is based on molar thermodynamic data and mass-action kinetics, providing a physically-based and flexible means for complex reaction pathways. Herein, we introduce a new thermodynamic class for intercalation materials into the open-source software. We discuss the derivation of molar thermodynamic data from experimental half-cell potentials, and provide practical guidelines. We then demonstrate the new class using a single-particle model of a lithium cobalt oxide/graphite lithium-ion cell, implemented in MATLAB. With the present extensions, Cantera provides a platform for the lithium-ion battery modeling community both for consistent thermodynamic and kinetic models and for exchanging the required thermodynamic and kinetic parameters. We provide the full MATLAB code and parameter files as supplementary material to this article.
The durability of polymer electrolyte membrane fuel cells (PEMFC) is governed by a nonlinear coupling between system demand, component behavior, and physicochemical degradation mechanisms, occurring on timescales from the sub-second to the thousand-hour. We present a simulation methodology for assessing performance and durability of a PEMFC under automotive driving cycles. The simulation framework consists of (a) a fuel cell car model converting velocity to cell power demand, (b) a 2D multiphysics cell model, (c) a flexible degradation library template that can accommodate physically-based component-wise degradation mechanisms, and (d) a time-upscaling methodology for extrapolating degradation during a representative load cycle to multiple cycles. The computational framework describes three different time scales, (1) sub-second timescale of electrochemistry, (2) minute-timescale of driving cycles, and (3) thousand-hour-timescale of cell ageing. We demonstrate an exemplary PEMFC durability analysis due to membrane degradation under a highly transient loading of the New European Driving Cycle (NEDC).
Lithium-ion batteries exhibit a well-known trade-off between energy and power, which is problematic for electric vehicles which require both high energy during discharge (high driving range) and high power during charge (fast-charge capability). We use two commercial lithium-ion cells (high-energy [HE] and high-power) to parameterize and validate physicochemical pseudo-two-dimensional models. In a systematic virtual design study, we vary electrode thicknesses, cell temperature, and the type of charging protocol. We are able to show that low anode potentials during charge, inducing lithium plating and cell aging, can be effectively avoided either by using high temperatures or by using a constant-current/constant-potential/constant-voltage charge protocol which includes a constant anode potential phase. We introduce and quantify a specific charging power as the ratio of discharged energy (at slow discharge) and required charging time (at a fast charge). This value is shown to exhibit a distinct optimum with respect to electrode thickness. At 35°C, the optimum was achieved using an HE electrode design, yielding 23.8 Wh/(min L) volumetric charging power at 15.2 min charging time (10% to 80% state of charge) and 517 Wh/L discharge energy density. By analyzing the various overpotential contributions, we were able to show that electrolyte transport losses are dominantly responsible for the insufficient charge and discharge performance of cells with very thick electrodes.
Mass transfer phenomena in membrane fuel cells are complex and diversified because of the presence of complex transport pathways including porous media of very different pore sizes and possible formation of liquid water. Electrochemical impedance spectroscopy, although allowing valuable information on ohmic phenomena, charge transfer and mass transfer phenomena, may nevertheless appear insufficient below 1 Hz. Use of another variable, that is, back pressure, as an excitation variable for electrochemical pressure impedance spectroscopy is shown here a promising tool for investigations and diagnosis of fuel cells.
Silicon (Si) has turned out to be a promising active material for next‐generation lithium‐ion battery anodes. Nevertheless, the issues known from Si as electrode material (pulverization effects, volume change etc.) are impeding the development of Si anodes to reach market maturity. In this study, we are investigating a possible application of Si anodes in low‐power printed electronic applications. Tailored Si inks are produced and the impact of carbon coating on the printability and their electrochemical behavior as printed Si anodes is investigated. The printed Si anodes contain active material loadings that are practical for powering printed electronic devices, like electrolyte gated transistors, and are able to show high capacity retentions. A capacity of 1754 mAh/gSi is achieved for a printed Si anode after 100 cycles. Additionally, the direct applicability of the printed Si anodes is shown by successfully powering an ink‐jet printed transistor.
Battery degradation is a complex physicochemical process that strongly depends on operating conditions. We present a model-based analysis of lithium-ion battery degradation in a stationary photovoltaic battery system. We use a multi-scale multi-physics model of a graphite/lithium iron phosphate (LiFePO4, LFP) cell including solid electrolyte interphase (SEI) formation. The cell-level model is dynamically coupled to a system-level model consisting of photovoltaics (PV), inverter, load, grid interaction, and energy management system, fed with historic weather data. Simulations are carried out for two load scenarios, a single-family house and an office tract, over annual operation cycles with one-minute time resolution. As key result, we show that the charging process causes a peak in degradation rate due to electrochemical charge overpotentials. The main drivers for cell ageing are therefore not only a high state of charge (SOC), but the charging process leading towards high SOC. We also show that the load situation not only influences system parameters like self-sufficiency and self-consumption, but also has a significant impact on battery ageing. We assess reduced charge cut-off voltage as ageing mitigation strategy.